Production of dialdehydes and conversion products thereof



United States No Drawing. Application November 12, 1953 Serial No. 391,724

Claims priority, application Germany December 31, 1951 20 Claims. (Cl. 260617) This invention relates to the production of dialdehydes and conversion products thereof and is a continuation-inpart of U. S. application, Serial No. 327,661, filed December 23, 1952, now abandoned.

Carbon monoxide and hydrogen have been added to compounds having two non-conjugated olefinic double bonds by treating such compounds with carbon monoxide and hydrogen in the presence of cobalt or other catalysts under suitable conditions of pressure and temperature.

These addition reactions did not prove valuable, however, since either the yield of bivalent derivatives was small or the primary reaction products were not sizable.

If carbon monoxide and hydrogen are added to diolefins, all or a predominant portion of the addition occurs at one of the two double bonds. it is for this reason that this reaction is not suitable for the production of dialdehydes. In the reaction dialdehydes are, at best, only partially formed, and reaction conditions are so unfavorable that any initially formed dialdehydes continue to react and form higher molecular by-products such as, for example,

resins, due to their extreme sensitivity. (See FIAT Report No. 1000, page 31, and FIAT Review, volume 36, 1, page 168, 1948.)

One object of this invention is the production of dialdehydes or conversion products thereof such as diols by the catalytic addition of carbon monoxide and hydro gen to hydrocarbons having at least 2 unsaturated double bonds. Thisand still further objects will become apparent from the following description:

It has now, very surprisingly, been found that very excellent yields of dialdehydes may be obtained from hydrocarbons having at least two olefinic bonds by the catalytic addition of water gas using as catalysts cobalt compounds supplying cobalt carbonyl hydrogen and effecting the addition in the presence of diluting agents, polymerization inhibitors, and stabilizers. The molecular size of the diolefinic hydrocarbons being processed must be at least such that no conjugated double bonds are present. Apart from this, the double bonds may have any position in the molecule.

The process may particularly advantageously be carried out with the use of cyclic diolefins, in which case these hydrocarbons may contain one or several rings.

In accordance with the invention, the formation of dialdehydes is either completely or extensively effected, and the undesirable side reaction of the sensitive dialdehydes is prevented. In addition to the cobalt compounds supplying cobalt carbonyl hydrogen as the catalysts, metallic cobalt or iron may be used if necessary or desired. Metallic cobalt or such organic or inorganic cobalt salts which contain no oxygen of oxidizing action may be used as the compounds supplying cobalt carbonyl. Unsuited for the formation of carbonyls are, for example, cobalt nitrate or cobalt bichromate.

Aromatic hydrocarbons, substituted aromatics and by droaromatics may be used as the diluting agents. Aliphatic hydrocarbons may also be used for this purpose,

"ice

With the use of aromatic hydrocarbons as diluting agents, monomeric dialdehydes are formed, whereas if aliphatic hydrocarbons are used as the diluting agents under iden tical reaction conditions, resinified dialdehydes are some times produced.

It has been found particularly advantageous to use a diluting agent which is miscible with the starting diolefin, but which is substantially immiscible with the reaction product obtained, which is methylated at both double bonds.

When using solid or gaseous catalysts, two layers are generally obtained as the reaction product, the upper of which generally contains the diluting agent and the lower of which contains the dialdehyde compound. The memo aldehyde compound which is also formed during the reac tion, will generally dissolve in the diluting agent. When using aqueous inorganic cobalt as the basic catalyst material, the reaction product is obtained in the form of three layers after filtration. The middle layer consists of the catalyst solution. The lower layer consists of the dialdehydic reaction product, while the upper layer comprises the diluting agent.

A further advantage in the use of diluting agents which are miscible with the starting diolefin and substantially immiscible with the dialdehydic reaction product resides in the fact that the diluting agent may be separated from the reaction product and the catalyst solution by simple decantation. Without the use of this particular type of diluting agent, separation is only possible by distillation. Further, the use of these diluting agents eliminates the necessity of carrying along the diluting agent through further processing steps as otherwise required, which necessitates the use of enlarged reaction spaces, as, for example, in the hydrogenation of aldehydic raw products to form the corresponding alcohols.

Parafiin hydrocarbons, which boil between 30-150 C. at 760 mm. Hg pressure, and, in particular, heptane, have been found preferable as diluting agents, which are miscible with the starting diolefin as, for example, dicyclopentadiene and substantially immiscible with the dialdehydic reaction product, as, for example, the tricyclodecane-dimethylal.

The diluting agent may be reused, if desired. It is, however, advantageous under certain conditions to process the monoaldehyde contained therein. Thus, for example, the monoaldehyde may be recovered, as, for example, by distillation, converted into the corresponding alcohol by the catalytic addition of hydrogen, and converted into the corresponding carboxylic acid by oxidation. It is also possible to effect a condensation reaction with the monoaldehyde such as an aldolization esterification and etherization.

It may be desirable in individual cases to treat the layer of diluting agent with hot water under pressure at a temperature of about l60-200 C. to thereby decompose the methyl carbonyl compounds and/or acetals dissolved therein.

In the case of the diluting agents which are miscible with the diolefinic starting material and substantially immiscible with the dialdehydic reaction product, the monoaldehyde concentration in the diluting agent should not be allowed to become too high, since larger quantities of monoaldehyde may act as dissolving intermediaries for the dialdehyde, thus making the separation into layers in the sense described above impossible. If, in the production of tricyclodecane dimethylol from dicyclopentadiene, the monoaldehyde component in the diluting agent is maintained, for example, below 10-20%, then a smooth separation of two or three layers will occur in the manner described above.

An incipient polymerization of the hydrocarbons hay- 3 1 ing at least 2 olefinic bonds may be' prevented by th addition of metallic cobalt or iron in the form of powder, finely divided iron. The metals used as polymerization individed form. Of particular 'advanta'ge is the use of finely divided iron. The metal used as polymerization inhibitors are employed ina quantity of 5-50 grams and preferably of 10'grams per kg. of starting material.

For the production of dialdehydes in accordance with the invention, the maintaining of a-sufiicientlylowreactiontemperature is of prime importance. Thus, for example, if cobalt in a finely divided and reduced state is used as a catalyst for the water gas addition, then the reaction temperature must be below 120 C., the rnost suitable -temp'eratu're'being 110- C. in this case. If a temperature above this, as, for example, 140 C.-1-5 C. is used, resinification Willoccur. If other catalysts, such as aqueous cobalt sulfate solutions, are used for the water gas addition, then temperatures which are generally somewhat higher are used.; In this-case, the reaction temperature must be below 170 C., the preferred 7 temperature, which allows the successful formation of dialdehydes being ISO-160 C. Substantially higher temperatures, however, may produce hydrogenating actions.- a

The carbon monoxide to hydrogen ratio of the gases used for the formation of dialdehydes ranges between 0.7 and Z- parts by volumeCO per part-by volume H Of particular advantage 'is the use of gases in which 1.5

parts by volume of carbon monoxide are contained per part by volume of hydrogen. An excess of carbon monoxide is advantageous because 4 molecules of C0 are consumed for each hydrogen atom in the formation-of cobalt carbonyl. An excess pressure of 150-300 kg./sq. cm, and preferably of 250-300 kg./.sq. cm. is used during the water-gas addition.

About 0.5-5 grams of cobalt in the form of cobalt 'carbonyl compounds, and preferably 1.5-2.5 gramsof cobalt in the form ofcobaltcarbonyl compounds are used perkgofstartingproduct. 7

It has been found of great advantage, in accordance with the invention, to add stabilizers tolthe mixture of substances chargedfor the purposeofstabilizing the dibeing 0.1%. The effect of these stabilizers is'toprevent' a polymerizationand to stabilize the dialdehydes produced,- a

-Yields' of atleast 50%and frquentlyudf '70%x and more of dialdehydes or their derivativesare obtained,iin'

accordance with the invention. Byi further oxidation, dicarboxylic acids or ,diestersmay'also be obtained as 'derivatives of the dialdehydes producedin accordance with the invention. dialdehydes or diols could at best be produced in yields of 15-35%. I

If, injaccordance with the invention, it is .desired to recover the dialdehydes, then the raw reaction products should be subjected to a treatmentwith pressure water: for theremoval of the dissolved metalfland to splitany acetals formed. If the hydrogenatio'n 'ofithe aldehydes is desired to form diols, then the above-mentionedtreatment with pressure watermay be combined withthe hydrogenation in single operational step. The treatment with water shouldprefe'rably be" effected at a temperature of -about l60f'"C.'to 200C. 'Du'riingf'this treatmentjwith water a pressure develops which is"-dependen t on the water vapor pressure valid for the temperature'used "and'onfthevapor pressure of the solvent'used. In general, this treatment 0 with water is carried out at carried out in the simultaneous presence of diluting agents,

side re- The process in accordance with the invention must be As contrasted to this in the prior art,

'4 polymerization inhibitors and stabilizers. tion inhibitors are understood to be substances which prevent the diolefinic hydrocarbons used as the starting material from polymerizing with themselves, i. e. from forming di-, trior still higher polymers- In this way resinification of the reaction products is to be prevented as far as possible. Stabilizers are understood to be substances which protect the aldehydes forming by the catalytic addition of water gas from oxidation, disproportionation and spontaneous decomposition. Examples of suitable polymerization inhibitors are metals, especially iron, cobalt or copper. Most suitable as stabilizers are organic dioxy compounds, preferably hydroquinone or substituted hydroquinones.

Hydrocarbons, especially benzene, toluene, xylene, cyclohexane, hexane, methyl cyclohexane, heptane, octane and still higher homologues are used as diluting agents. These diluting agents must be added in a proportionpf at least 1:1. Most suitable is the addition of 4. parts by volume of diluting agent per part by volume of starting material. With regard to the'subsequentseparation of the diluting agent, this should have an-upper boiling limit of about 200 C. It is also possible touse solvents which after the reaction form a layer on' top of the reaction products thus permitting their separation.

Suitable solvents are, for example, hexane and higher hydrocarbons.

The reaction temperatures in the water gas' addition range between and 180 C. When operating with 'rnetallic catalysts, temperatures of '100-120" C. are

preferably used. If-the catalysts consist of cobalt salts,

temperatures of to C. must be used.

The pressures must be in excess of l'50'kg./sq. cm. The upper limit of the pressures is only set by the resistivity of the reaction vessels, 'it beingpo'ssible to use pressures of as high as 1000 kg./sq.jcm;"and stilljhigher.

Further details may be seen from thefcill'o'wing examples which are given by way off illustration'and not limitation.

Example 1 700 cc. of a reaction mixture consisting of 200cc.

of dicyclopentadiene stabilized with 0.5 grns. i'hydroquinone, 300 cc. of benzene, and 200 cc. of an aqueous solution which contained 'per liter l5..gms.aof;;cobalt in the form of cobalt sulfate and 30; gIIIS.'TOf magnesia (MgO) in the form of magnesium sulfate Was'filledinto.

an autoclave of 2.3 liters capacity provided with-amagnetic stirrer. After the addition of3 gms. of ferrum rcductum to this mixture, the autoclave was closed- From a steel bottle, water gas containing 1.2 partsby volume, of

hydrogen'per part by volume of carbonfmonoxide was introduced to the autoclave until a pressure of 180 kilos/sq. cm. was reached. Thereafter, thestirrer was started and the autoclave was heated up; At a temperature of 140 C., no furtherincrease-inpressure could be observed, but a pressure drop occurred. :Within 120 rninues, 104 kg./sq..cm. of water gas, approximately of water, and heated within the autoclave to about 200 C., thereby splitting up any acetals present and precipitat: ing the metalcarbonyls dissolved. -Afterthe s p rfifi n I of the water, the reaction product was distilled. After having driven off the solvent, the main fractiomaamounting to 60% by weight of the dicyclopentadiene charged,

was obtained between "C. to C; at 'a=press'urc of '10 mm. Hg. This characteristics:

main fraction had the following Polymeriza- Molecular weight 210 Iodine number, I. N 19 Neutralization number, N. N 0.5 Ester number, E. N 39 Hydroxyl number, OH N 43 Carbonyl number, CO N 435 These characteristics indicated that the reaction product had the composition as shown on the following table:

te ses 6 l80-210 C 37% by weight diol. 210-230 C 6% by weight diol containing 20% ester. Above 230 C 37% by weight esters, aldols, resins.

Example 4 By means of cold benzene, a polymerization product was extracted from a polymeric mixture of dicyclopenta- Wt. M01. Proportionate percent Substance Wt. I. N. 00 N. OH N. E. N.

I. N. GO N. OH N E. N

12. 1 Unsaturated m on 0 a1 d e 162 157 345 19 41 1 Average.

Example 2 diene, which polymerization product had the following The reaction mixture used in Example 1 was separated, after completed gas absorption, from the catalyst solution by decantation and filled again into the autoclave which had previously been charged with cc. of re duced nickel hydrogenation catalyst and 200 cc. of water. At a hydrogen pressure of about 50 kilos/sq. cm., the

reaction mixture was treated at C. to 100 C. until constancy of pressure occurred. After the completion of the hydrogenation, the oily constituents were separated from the water and from the catalyst and subsequently distilled. An apparatus operating with short distfllation paths and a heatable receiver were used for the distillation. After the separation of the benzene, the following fractions were obtained:

The total yield of diol was approximately by weight.

Example 3 By means of the apparatus used in Example 1, 500 cc. of a dicyclopentadiene-benzene mixture containing 3 parts by volume of benzene for every 2 parts by volume of dicyclopentadiene and being stabilized with 0.1% of hydroquinone were treated with water gas with the use of cc. of reduced cobalt-magnesia-kieselguhr catalyst under the conditions as used in Example 1. The catalyst contained 10 parts of magnesia and 200 parts of kieselguhr for every 100 parts of cobalt. Already at 100 C. a gas absorption occurred, so that a temperature of C. did not have to be exceeded. With a free gas space of 1.5 liters remaining in the autoclave, 100 kilos/sq. cm. of water gas were absorbed within 30 minutes. After cooling to 60 C., the gas was blown off and the reaction mixture was charged with 200 cc. of water, which was injected by means of nitrogen. While stirring the mixture, it was heated to a temperature of 180 C. and maintained for 30 minutes at this level. After cooling, the reaction mixture was separated from the water and hydrogenated as described in Example 1. In the distillation, which was carried out as in Example 1, the following products were obtained at a pressure of 2 mm. Hg:

Below 180 C 20% by weight monol containing 20% diol.

characteristics:

iodine number 188 Molecular weight 225 Pour point C. +72

These data indicate that a polymerization product was present which contained 4 molecules of cyclopentadiene.- 200 grams (0.785 mole) of this product were dissolved in 300 grns. toluene and filled into a pressure vessel of 2020 cc. capacity. Into the same pressure vessel there were given 300 cc. of an aqueous solution which contained in the form of sulfates 15 grams per liter of cobalt and 25 grams/liter of magnesium oxide and, moreover, 10 grams of iron powder, 0.2 gm. hydroquinone and 0.02 gm. alkyl aryl sulfonate. Thereafter, the pressure vessel was closed. While constantly stirring, water gas consisting of approximately equal parts by volume of carbon monoxide and hydrogen was introduced to the pressure vessel at a temperature of -155 C. until a pressure of 280 kilos/sq. cm. was reached. After a treating period of 60 minutes, the water gas pressure had dropped to 188 kilos/sq. cm., which corresponded to a carbon monoxide-hydrogen absorption of 69 standard liters.

The reaction product had a volume of 610 cc. and was freed from its metal content by means of 5% hydrochloric acid. Thereafter, it had the following character- This product was treated for two hours :at 220-4500 C. with hydrogen in the presence of a cobalt-thorium oxide-kieselguhr catalyst with the addition of 100 cc. of water. The final product obtained was a two-component mixture from which the thinly liquid portion consisting of toluene could be separated by means of a suction filter. The viscous residue was dissolved at 6070 C. in twice the quantity of ethanol and separated from the catalyst by filtration. Thereafter, the solvent was removed by evaporation.

As final product, 169 grams of a varnish-like viscous thick oil were obtained, which had the following characteristics:

Iodine number 3 Neutralization number 2 Ester number 2 Hydroxyl number 340 Carbonyl number 1 '75 jPour point C 83 I were mixed with 1500 cc. cyclohexane. H given into a pressure vessel and diluted with 100 cc. of

1288 grams of a dipentene mixture having the characteristics:

This liquid was an aqueous cobalt sulfate solution which contained per liter grams of cobalt and grams of magnesium oxide in the form of their sulfates. Moreover, 2 gms. hydroquinone, 100 gms. of powdered iron and 0.2 gms. of alkyl aryl sulfonate were added. While constantly stirIing ater gas was passed into the pressure vessel at 160?.Cguntil a pressureof 300 kilos/sq. crn. was reached. After a treating period of 3 hours 540 standard liters (CO+H had been absorbed.

Afterthe water gas addition, the aldehydic product was separated from the catalyst solution and the iron slurry by filtration. After the addition of 300 cc. of a catalyst which consisted of 100 parts of cobalt metal, 10 parts of magnesium oxide, 5 parts of thorium oxide and 200 parts of lrieselguhr, theproduct was hydrogenated at '190200 C- and a pressure of 100150 kilos/sq. cm. with a nitrogen-hydrogen mixture consisting of 70% H and N After the separation of the catalyst, the alcohol formed was distilled.

At first the first runnings consisting of cyclohexane and terpane methylol distilled over. Then, at a pressure of 1.5 mm. Hg and a temperature between 157 C. and 176 C., ,a highly viscous ,'clear fraction was obtained from which, on cooling, a small quantity of a thinly liquid upper layer separated, which was soluble in low hydrocarbons. This layer had the following characteristics:

Density at 20 C 0.907 Refractive index, 11 1.475 l-lydroxylnumberua 11 Iodine number V 15 These data indicate that a mixture of unsaturatedand saturated ethers was present.

The bulk of the highly viscous fraction distilled over at 1.5 mm. Hg had rthe following characteristics:

V In thepure form, terpane dimethylol C H O has a calculated hydroxyl number of 560. Thus, the highly viscous fraction consisted of 96.4% terpane dimethylol.

Example 6 V a 1,000 cc. dicyclopentadiene (7.4 mols), 1.500 cc.-heptane, 1,000 cc. cobalt sulfate-magnesimn sulfate solution containing .15 grams .Co/liter and 15 grams MgO/liter, grams .ferrum .reductum, .1 gram "hydroqu'ino'ne, and 0.2 gramualkylarylsulfonate were placed into an autoclave :of 9.5.7.1iterscapacity provided with stirrer. Watergas .was .then pressed. in .untila pressureof 195 atmospheres was reached.vv The autoclave was heated to Density at 20 C 0.859.

Refractive index, n 1.4873.

Boiling point -120" C. (100 mm. Hg). 7 Ozone iodine number 327.

of water.

and maintained for 1% hours at this tempera ture while making up the pressure to 180 atmospheres. During: this time, atmospheres of water gas were absorbed=640 normal liters=28.5 mols- CO+H The calculated gas quantity is 29.7 mols CO-l-H After cooling to about 30 C., the reaction product was dis: charged and formed three layers after filtration:

1480 cc. heptane layer having a carbonyl number of 60 and a density at 20 C. of 0.685,

1110 gins. viscous dialdehyde layer having an iodine number of 29, a carbonyl number of 380 and a hydroxyl number of 64, 940 cc; catalyst solution.

The heptane layer was heated for two hours in the autoclave with 10% by volume of water. at 200 C., separated after cooling from the water, and filtered- By this treatment, the heptane layer, which contained about 1.0 gram Co and 0.2 gram Fe/liter, and was of a brown; red color, became light yellow and metal-free. In this state, the diluent may be used again. The dialdehyde layer was mixed with 110 cc. of reduced carbon monoxide hydrogenation catalyst and subjected to a hydrating hydrogenation at 230 C. in the presence of 200 cc. 7 The carbon monoxide hydrogenation catalyst consisted, for example, of 100 parts of cobalt metal, 10 parts of magnesium-oxide, 5 parts of thorium oxide, and 200 parts of kieselguhr. The raw diol obtained was metal-free, while about 5 grams Co/liter and 2 grams Fe /liter were contained in the raw'diol charged.

After fractional distillation there were obtained:

122 grams tricyclodecane-methylol, 690 grams tricyclodecane-dimethylol,

78 grams of a resin-like residue consisting polyesters, and polymeric alcohols.

Example 7 1,000 cc. dicyclopentadiene and 1,500 cc. heptanewere subjected to the dialdehyde synthesis effected with 50.

grams carbon monoxide hydrogenation catalyst, at a temperature of 110 C., a water gas pressure of 260 atmospheres, and with the addition of 1 gram hydroquinone.

The reaction productforrned two layers which werev sep.

200 cc. of water.

arated by decantation. There were obtained 1450 cc. heptane layer and V 1160 grams raw dial layer with the catalyst suspended therein.

The heptane layer was treated with water gas at C. without the further addition of catalyst, and subsequently heated for half an hour at200 C. with the addition of arated from the water, filtered off from the metallic hydroxide deposits, separated in flakes, and fractionated. After having distilled oi the heptane, there remained 120 grams of higher boiling products which consisted of tricyclodecane-methylol, 11% tricyclodecane-climethylol, and 13% dicyclopentadiene-polymers; The heptane distilled ofl? was again used for a new batch.

The raw diallayer was diluted with the same volume of 80% ethanol and hydrogenated with hydrogen at 220 C. until the carbonyl number had disappeared. There was obtained a raw diol of a faintly yellow color, which, on distillation under-vacuum from a vessel having a packed column of 30 cm. in heightQyielded the following fractions:

75180 C.- at 2 mm. Hg: 220 grams tricyclo'decane. dimethylol first runnings (cyclopentanermethylol, .tjricyclodecane methylol, tricyclodecane+homologues),-.

180.200 C. at 1.5 mm. Hg: 590 grams tricyclode'canee dimethylol main fraction, 1

Above 200 C. at 1.5mm. Hg: 300 grams residue (solid resin-like products,'melting point 100-120 .C.);. Example ,8 a

The same mixture as used in Example 6 was, after f e ters.

After cooling, the product was septhe addition of water gas, separated into three layers by decantation. The heptane layer was mixed with 0.5% manganese butyrate and treated at 4050 C. with molecular oxygen. After 4 hours, about 80% of the carbonyl number was converted into acid number. The product was subjected to a mild hydrogenation. In the distillation, after having driven oif the solvent, there were obtained at 145 C. under 0.7 mm. Hg 80 grams tricyclodecane-carboxylic acid as a syrupy liquid which, after standing for a short time, crystallized well, melted between 45 and 55 C., and had an acid number of 311.

The dialdehyde layer was mixed with the same volume of toluene and freed from its metal content by washing with a aqueous hydrochloric acid at 50 C. After the removal of the acid by washing with water, the purified raw dialdehyde was fractionated. The following fractions were obtained at 1.5 mm. Hg:

The dialdehyde obtained is a liquid of low viscosity and a faintly yellow color and somewhat pungent odor which suggests lower fatty acids. It had the following characteristics:

Density at C 1.142 Refractive index, r1 1.5260 Carbonyl number 505 Iodine number 5 According to these values, the product contained about 87% tricyclodecane-dimethylal.

We claim:

1. Process for the production of dialdehyde and conversion products thereof, which comprises contacting a hydrocarbon having at least two non-conjugated olefinic bonds with a carbon monoxide hydrogen-containing gas in the presence of a cobalt compound supplying cobalt carbonyl hydride, a hydrocarbon-diluting agent, a polymerization inhibitor, and a stabilizer, and recovering a dialdehydic reaction product.

2. Process according to claim 1, in which said hydrocarbon-diluting agent is a saturated hydrocarbon substantially miscible with said hydrocarbon having at least two non-conjugated olefinic bonds and substantially immiscible with said dialdehydic reaction product.

3. Process according to claim 1, in which said hydrocarbon-diluting agent is selected from the group consisting of aromatic hydrocarbons and hydro-aromatic hydrocarbons.

4. Process according to claim 1, in which said polymerization inhibitor is selected from the group consisting of metallic cobalt and metallic iron.

5. Process according to claim 4, in which said polymerization inhibitor is present in amount of about 5-50 grams per kilogram of starting material.

6. Process according to claim 1, in which said stabilizer is an aromatic oxy compound.

7. Process according to claim 6, in which said stabilizer is hydroquinone.

8. Process according to claim 7, in which said stabilizer is present in the amount of 0.011% by weight of the starting material.

9. Process according to claim 1, in which said compounds supplying cobalt carbonylhydride is present in amount to 0.5-5 grams per kilogram of starting material.

10. Process according to claim 1, in which said cobalt compound supplying cobalt carbonyl hydride is a member selected from the group consisting of metallic cobalt and reduced cobalt compounds, and in which said contacting is efiected at a temperature of about -120 C.

11. Process according to claim 1, in which the reaction products of said contacting are contacted with water at a temperature of about 200 C. for the freeing of aldehydes contained therein of their contents of metals and acetals.

12. Process according to claim 1, in which said diluting agent is a saturated hydrocarbon substantially miscible with said hydrocarbon having at least two nonconjugated olefinic bonds and substantially immiscible with said aldehydic reaction product, and in which said diluting agent and said aldehydic reaction product are separated after said contacting by layer formation.

13. Process according to claim 12, in which the separated diluting agent is contacted with Water at a temperature of about 160200 C. for the freeing thereof of metals and acetals.

14. Process according to claim 13, in which said diluting agent is a paraffin hydrocarbon having a normal boiling point between 30150 C.

15. Process for the production of tricyclodecane-dimethylol which comprises contacting dicyclopentadiene with a carbon monoxide hydrogren-containing gas in the presence of a cobalt compound supplying cobalt carbonyl hydride, a polymerization inhibitor, a stabilizer and a saturated hydrocarbon-diluting agent substantially miscible with said dicyclopentadiene and substantially immiscible with said tricyclodecane-dimethylol, and recovering tricyclodecane-dimethylol.

16. Process according to claim 15, in which said saturated hydrocarbon diluting agent and said tricyclodecane-dirnethylol are separated by layer formation.

17. Process according to claim 16, in which said saturated hydrocarbon diluting agent is recycled in the process after said separation.

18. Process according to claim 15, in which said hydrocarbon diluting agent is a paraffin hydrocarbon normally boiling between 30150 C.

19. Process according to claim 18, in which said diluting agent is heptane.

20. Process according to claim 15, in which said diluting agent is separated from the reaction products by layer formation, and recycled.

References Cited in the file of this patent UNITED STATES PATENTS 2,462,448 Whitman Feb. 22, 1949 2,517,383 Brooks Aug. 1, 1950 2,738,370 Staib et al. Mar. 13, 1956 FOREIGN PATENTS 660,737 Great Britain Nov. 14, 1951 OTHER REFERENCES Adkins et al.: J. Org. Chem., vol. 17, July 1952, pp. 980-987.

UNITED STATES PATENT TTTQE CERTIFICATE @F QORRECTIQN Patent No, 2350,5362 September 2, 1958 Karl Biielmer et all,

It is hereby certified that error appears in the printed epeoifieation of the above numbered patent requiring" correction and that the said Letters Patent should read as corrected below,

Column 3 line 2, after powdery" insert filings shavings, or the like, or in any other suffieiently line 3, strike out "finely divided iron, The metals used as polymerization ir line 5 for "metal" reed metals column 7, line 68, for "10500 0a., reed 1,500 ecu column 8, line 29, for "diol" read dial Signed and sealed this day of November 1958a (SEAL) Attest:

KARL AXLINE ROBERT C. WATSON Attesting Qfi'icer Commissiener of Patents 

1. PROCESS FOR THE PRODUCTION OF DIALDEHYDE AND CONVERSION PRODUCTS THEREOF, WHICH COMPRISES CONTACTING A HYDROCARBON HAVING AT LEAST TWO NON-CONJUGATED OLEFINIC BONDS WITH A CARBON MONOXIDE HYDROGEN-CONTAINING GAS IN THE PRESENCE OF A COLBALT COMPOUND SUPPLYING COBALT CARBONYL HYDRIDE, A HYDROCARBON-DILUTING AGENT, A POLYMERIZATION INIHIBITOR, AND A STABILIZER, AND RECOVERING A DIALDEHYDIC REACTION PRODUCT. 